TWI646156B - Curable polyoxynoxy composition and optical semiconductor device - Google Patents

Abstract

The curable polysiloxane composition of the present invention has excellent adhesion to optical semiconductor elements, lead frames, substrates, bonding wires, and the like in optical semiconductor devices, and includes at least: (A) organic polysiloxane, which is a Has at least 2 alkenyl groups bonded to silicon atoms in the molecule; (B) Organic hydrogenated polysiloxane, which has at least 2 hydrogen atoms bonded to silicon atoms in one molecule; (C) Triazole compounds (D) metal-based condensation reaction catalyst; and (E) catalyst for hydrosilylation reaction. The optical semiconductor device of the present invention is an optical semiconductor device in which the optical semiconductor device is sealed or coated with a cured product of the composition, and has excellent reliability after a moisture absorption reflow test.

Description

Curable polysiloxane composition and optical semiconductor device

The present invention relates to a curable polysiloxane composition and an optical semiconductor device using the same.

The hydrosilylation reaction-hardening polysilicone composition is used as a photocoupler because it forms a hardened material with excellent weather resistance, heat resistance, and other properties. It is rapidly hardened by heating and does not produce by-products during hardening. Sealant, protector, or adhesive for optical semiconductor devices such as light-emitting diodes and solid-state imaging devices.

However, due to the insufficient adhesiveness of the hydrosilylation-curable polysiloxane composition, for example, Japanese Patent Laid-Open No. 2009-256603 proposes a hardenable polysiloxane composition containing vinyl groups at both ends of a molecular chain A linear organic polysiloxane, an organic hydrogenated polysiloxane having at least two hydrogen atoms bonded to silicon atoms in one molecule, a metal-based condensation reaction catalyst, a platinum group metal-based addition reaction catalyst, And an organopolysiloxane containing at least two functional groups selected from the group consisting of alkenyl, alkoxy, and epoxy groups, and then a component; and Japanese Patent Laid-Open No. 2010-043136 proposes the following hardening polysilicon Oxygen composition: It comprises a polysiloxane having at least 2 alkenyl groups bonded to a silicon atom, a polysiloxane crosslinking agent having at least 2 hydrogen atoms bonded to a silicon atom, and a member selected from the group consisting of At least one organometallic compound in the group consisting of an organic zirconium compound, an organic zinc compound, an organic magnesium compound, and an organic potassium compound having an atomic number of 3 or more.

However, there is a problem that, even with such a hardening polysiloxane composition, the adhesiveness to optical semiconductor elements, lead frames, substrates, bonding wires, and the like in optical semiconductor devices is insufficient. When the obtained optical semiconductor device is subjected to a moisture absorption reflow test, peeling occurs between the optical semiconductor element, the lead frame, the substrate, or the bonding wire and the cured product of the composition.

On the other hand, Japanese Patent Application Laid-Open No. 2009-215434 proposes a curable polysiloxane composition containing an organic polysiloxane having at least two aliphatic unsaturated bonds in one molecule and not containing an aromatic hydrocarbon group. Alkanes, organic hydrogenated polysiloxanes having at least two hydrogen atoms bonded to silicon atoms in one molecule, platinum group metal-based catalysts, and the organic polysiloxanes and organic hydrogenated polysiloxanes A total of 100 parts by mass of 0.05 to 5 parts by mass of benzotriazole-based Based, benzophenone based, benzoate based, hindered amine based photodegradation inhibitors.

However, this curable polysiloxane composition also has a problem of insufficient adhesion to optical semiconductor elements, lead frames, substrates, bonding wires, and the like in optical semiconductor devices.

[Prior technical literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. 2009-256603

Patent Document 2: Japanese Patent Laid-Open No. 2010-043136

Patent Document 3: Japanese Patent Laid-Open No. 2009-215434

An object of the present invention is to provide a hardenable polysilicone composition having good adhesion to an optical semiconductor element, a lead frame, a substrate, a bonding wire, etc. in an optical semiconductor device, and another object of the present invention is to provide a Optical semiconductor device with excellent reliability after moisture absorption reflow test.

The curable polysiloxane composition of the present invention is characterized in that it comprises at least: (A) an organic polysiloxane, which has at least two alkenyl groups bonded to silicon atoms in one molecule; (B) an organic hydrogenated polysiloxane Oxane, which has at least 2 hydrogen atoms bonded to silicon atoms in a molecule {relative to 1 mol of the alkenyl group bonded to silicon atoms in (A) component, and silicon atoms in this component are bonded to silicon atoms The amount of hydrogen atoms becomes 0.1 to 10 moles}; (C) a triazole-based compound (relative to the composition, an amount of 1 ppm to 0.5% by mass unit); (D) a metal-based condensation reaction catalyst ( (Equivalent to 20 ppm to 0.1% by mass unit with respect to the composition); and (E) a catalyst for a hydrosilylation reaction (amount to promote hardening of the composition).

The component (A) is preferably a general formula (A-1): R ¹ ₃ SiO (R ¹ ₂ SiO) _m SiR ¹ ₃

(In the formula, R ¹ is the same or different monovalent hydrocarbon group, in which at least two R ¹ in an molecule are alkenyl groups, and m is an integer of 5 to 1,000)

Straight-chain organic polysiloxane and / or (A-2) average unit formula: (R ¹ SiO _3/2 ) _a (R ¹ ₂ SiO _2/2 ) _b (R ¹ ₃ SiO _{1 / 2} ) _c (SiO _4/2 ) _d (XO _1/2 ) _e

(In the formula, R ¹ is the same as the above, wherein 0.01 to 50 mole% of the total of R ¹ is an alkenyl group, X is a hydrogen atom or an alkyl group, and a, b, c, d, and e satisfy 0 ≦ a ≦ 1.0, 0 ≦ b ≦ 1.0, 0 ≦ c <0.9, 0 ≦ d <0.5, 0 ≦ e <0.4, and a + b + c + d = 1.0

The branched organic polysiloxane shown.

The component (C) is preferably a benzotriazole-based compound, and particularly preferably selected from the group consisting of benzotriazole, tolutriazole, carboxybenzotriazole, 1H-benzotriazole-5-carboxylic acid methyl ester, and At least one benzotriazole compound in the group consisting of nitrobenzotriazole.

The component (D) is preferably at least one selected from the group consisting of an organic aluminum compound, an organic titanium compound, an organic zirconium compound, an organic zinc compound, and an organic iron compound. Organic metal compounds.

The curable polysiloxane composition of the present invention is preferably a sealing agent or a coating agent for an optical semiconductor device.

The optical semiconductor device of the present invention is characterized in that the optical semiconductor element is sealed or covered by the hardened material of the above-mentioned curable polysiloxane composition, and the optical semiconductor element is preferably a light emitting diode.

The curable polysiloxane composition of the present invention is characterized by having excellent adhesion to an optical semiconductor element, a lead frame, a substrate, a bonding wire, and the like in an optical semiconductor device. The optical semiconductor device of the present invention is characterized by excellent reliability after a moisture absorption reflow test.

1‧‧‧optical semiconductor element

2‧‧‧lead frame

3‧‧‧lead frame

4‧‧‧ bonding wire

5‧‧‧ reflective material

6‧‧‧ Hardened product of hardening polysiloxane composition

FIG. 1 is a cross-sectional view of an LED as an example of an optical semiconductor device of the present invention.

First, the curable polysiloxane composition of the present invention will be described in detail.

(A) The component is an organopolysiloxane having at least two alkenyl groups bonded to a silicon atom in one molecule as a main agent of the composition. Examples of the alkenyl group include vinyl, allyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, and dodecyl An alkenyl group having 2 to 12 carbon atoms, such as an alkenyl group, is preferably a vinyl group. Examples of the (A) component other than the alkenyl group bonded to the silicon atom include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, third butyl, Alkyl, neopentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and other alkyl groups having 1 to 12 carbons; phenyl, tolyl , Xylyl, naphthyl and other aryl groups having 6 to 20 carbon atoms; benzyl, phenethyl, phenylpropyl and other arylalkyl groups having 7 to 20 carbon atoms; and by means of fluorine atom, chlorine A group in which a halogen atom such as an atom or a bromine atom is substituted for part or all of the hydrogen atoms of these groups. Moreover, as long as the objective of this invention is not impaired, the silicon atom in (A) component may have a small amount of hydroxyl groups, alkoxy groups, such as a methoxy group and an ethoxy group.

Examples of the molecular structure of the component (A) include a linear structure, a linear structure having a branch, a branched structure, a cyclic structure, and a three-dimensional network structure. The component (A) may be one type of organic polysiloxane having these molecular structures, or a mixture of two or more types of organic polysiloxane having such molecular structures.

Such (A) component is preferably (A-1) General formula: R ¹ ₃ SiO (R ¹ ₂ SiO) _m SiR ¹ ₃

Straight-chain organic polysiloxane and / or (A-2) average unit formula: (R ¹ SiO _3/2 ) _a (R ¹ ₂ SiO _2/2 ) _b (R ¹ ₃ SiO _{1 / 2} ) _c (SiO _4/2 ) _d (XO _1/2 ) _e

The branched organic polysiloxane shown.

In the component (A-1), in the formula, R ¹ is the same or different monovalent hydrocarbon group, and examples thereof include the same alkyl group, alkenyl group, aryl group, aralkyl group, and fluorine atom and chlorine atom. A group in which a halogen atom such as a bromine atom is substituted for part or all of the hydrogen atoms of these groups. Among them, at least two R ^{1 in} one molecule are alkenyl. In the formula, m is an integer of 5 to 1,000, preferably an integer of 50 to 1,000 or an integer of 100 to 1,000.

Examples of such a component (A-1) include dimethyl polysiloxane blocked at both ends of the molecular chain with dimethylvinylsiloxy, and dimethylvinylsiloxy at both ends of the molecular chain. Blocked dimethylsiloxane-methylvinylsiloxane copolymer, dimethylsiloxane-methylphenylsiloxane blocked at both ends of the molecular chain by dimethylvinylsiloxy Copolymer, methylphenyl polysiloxane blocked at both ends of molecular chain with dimethylvinylsiloxy, dimethylsiloxane-methyl blocked at both ends of molecular chain with trimethylsiloxy Vinylvinylsiloxane copolymer, dimethylsiloxane-methylvinylsiloxane-methylphenylsiloxane copolymer blocked at both ends of molecular chain by trimethylsiloxy group, and the like A mixture of two or more.

In the component (A-2), in the formula, R ¹ is the same or different monovalent hydrocarbon group, and examples thereof include the same alkyl group, alkenyl group, aryl group, aralkyl group, and fluorine atom, A group in which a halogen atom such as a chlorine atom or a bromine atom replaces part or all of the hydrogen atoms of these groups. Among them, 0.01 to 50 mole%, 0.05 to 40 mole%, or 0.09 to 32 mole% of the total of R ¹ is preferably an alkenyl group. The reason is that if the ratio of the alkenyl group is above the lower limit of the above range, the hardenability of the obtained composition is good. On the other hand, if the ratio of the alkenyl group is below the upper limit of the above range, the hardened product obtained The mechanical properties are relatively good. The content of the alkenyl group can be determined, for example, by analysis of a Fourier transform infrared spectrophotometer (FT-IR), nuclear magnetic resonance (NMR), or gel permeation chromatography (GPC).

In the formula, X is a hydrogen atom or an alkyl group. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, third butyl, pentyl, neopentyl, hexyl, cyclohexyl, heptyl, and octyl. , Nonyl, decyl, undecyl, dodecyl and the like having an alkyl group having 1 to 12 carbon atoms, and preferably an alkyl group having 1 to 3 carbon atoms.

In the formula, a is the ratio of the siloxane units represented by R ¹ SiO _3/2 and satisfies the number of 0 ≦ a ≦ 1.0, and b is the formula: R ¹ ₂ SiO _2/2 The ratio of siloxane units, and satisfies the number of 0 ≦ b ≦ 1.0, c is the expression: the ratio of siloxane units represented by R ¹ ₃ SiO _1/2 , and satisfies the number of 0 ≦ c <0.9, d is the expression: the ratio of the siloxane units represented by SiO _4/2 , and satisfies the number of 0 ≦ d <0.5. In the formula, a + b + c + d = 1.0. In addition, e represents a hydroxyl group or an alkoxy group bonded to a silicon atom, and satisfies the number of 0 ≦ e <0.4.

As (A) component, (A-1) component, (A-2) component, or a mixture of (A-1) component and (A-2) component can be used. In the case where a mixture of the (A-1) component and the (A-2) component is used, the content of the (A-2) component is preferably (A-1) in terms of better operability of the obtained composition ) And 90% by mass or less of the total amount of the component (A-2) or 60% by mass or less. In addition, in terms of the mechanical properties of the obtained hardened material being relatively good, the content of the (A-2) component is preferably at least 10% by mass of the total amount of the (A-1) component and the (A-2) component.

The component (A) is liquid or solid at 25 ° C. When the component (A) is liquid at 25 ° C, its viscosity at 25 ° C is preferably in the range of 1 to 1,000,000 mPa · s or in the range of 10 to 1,000,000 mPa · s. In addition, the viscosity can be based on JIS, for example, by using Measured by K7117-1 type B viscometer.

(B) The component is an organohydrogenpolysiloxane having at least two hydrogen atoms bonded to silicon atoms in one molecule of the crosslinking agent of the composition. Examples of the group bonded to the silicon atom other than the hydrogen atom in the component (B) include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, third butyl, and pentyl , Neopentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and other alkyl groups having 1 to 12 carbons; phenyl, tolyl, di Aryl groups having 6 to 20 carbons such as tolyl and naphthyl; aralkyl groups having 7 to 20 carbons such as benzyl, phenethyl, and phenylpropyl; and fluorine, chlorine, and A group in which a halogen atom such as a bromine atom replaces part or all of the hydrogen atoms of these groups. Moreover, as long as the objective of this invention is not impaired, the silicon atom in (B) component may have a small amount of hydroxy groups, alkoxy groups, such as a methoxy group and an ethoxy group.

As the molecular structure of the component (B), linear, branched linear, branched, cyclic, and three-dimensional network structures may be exemplified, and branched linear, branched, or Three-dimensional network structure.

(B) The component is solid or liquid at 25 degreeC. When the component (B) is liquid at 25 ° C, the viscosity at 25 ° C is preferably 10,000 mPa · s or less, within the range of 0.1 to 5,000 mPa · s, or within the range of 0.5 to 1,000 mPa · s . The viscosity can be determined by, for example, measurement using a B-type viscometer according to JIS K7117-1.

Examples of such (B) component include 1,1,3,3-tetramethyldisilazane, 1,3,5,7-tetramethylcyclotetrasiloxane, and tris (dimethyl hydrogen). (Silyloxy) methylsilane, tris (dimethylhydrosilyloxy) phenylsilane, 1-glycidoxypropyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1, 5-glycidoxypropyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1-glycidoxypropyl-5-trimethoxysilylethyl-1,3,5 , 7-tetramethylcyclotetrasiloxane, methyl hydrogen polysiloxane blocked at both ends of the molecular chain by trimethylsiloxy, dimethyl blocked at both ends of the molecular chain by trimethylsiloxy Siloxane-methylhydrosiloxane copolymer, dimethyl polysiloxane blocked at both ends of the molecular chain with dimethylhydrosiloxy, dimethylhydrosiloxy blocked at both ends of the molecular chain Dimethyl siloxane-methyl hydrosiloxane copolymer, methyl siloxane-diphenyl siloxane copolymer blocked at both ends of the molecular chain by trimethyl siloxane, molecular chain Methylhydrosilane-diphenylsilane-dimethylsilane copolymer blocked with trimethylsiloxy at both ends, containing (CH ₃ ) ₂ Copolymers of HSiO _1/2 units and SiO _4/2 units, copolymers containing (CH ₃ ) ₂ HSiO _1/2 units, SiO _4/2 units and (C ₆ H ₅ ) SiO _3/2 units, and these A mixture of two or more.

The content of the component (B) is 0.1 to 10 moles relative to the mole of the alkenyl group bonded to the silicon atom in the component (A). The amount is 0.5 to 5 moles. The reason is that if the content of the component (B) is below the upper limit of the above range, the mechanical properties of the obtained hardened material are relatively good. On the other hand, if it is above the lower limit of the above range, the hardened composition is hardened. Sex is better. The content of hydrogen atoms bonded to silicon atoms in the component (B) can be determined by, for example, a Fourier transform infrared spectrophotometer (FT-IR), nuclear magnetic resonance (NMR), or gel permeation chromatography (GPC). And so on.

(C) A component is a triazole-type compound which provides peeling resistance to the hardened | cured material of this composition. Examples of the component (C) include 1H-1,2,3-triazole, 2H-1,2,3-triazole, 1H-1,2,4-triazole, and 4H-1,2,4- Triazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, benzotriazole, tolutriazole, carboxybenzotriazole, 1H-benzotriazole-5-carboxyl Methyl ester, 3-amino-1,2,4-triazole, 4-amino-1,2,4-triazole, 5-amino-1,2,4-triazole, 3-mercapto- 1,2,4-triazole, chlorobenzotriazole, nitrobenzotriazole, aminobenzotriazole, cyclohexane [1,2-d] triazole, 4,5,6,7 -Tetrahydroxytolutriazole, 1-hydroxybenzotriazole, ethylbenzotriazole, naphthotriazole, 1-N, N-bis (2-ethylhexyl)-[(1,2,4 -Triazol-1-yl) methyl] amine, 1- [N, N-bis (2-ethylhexyl) aminomethyl] benzotriazole, 1- [N, N-bis (2-ethyl Hexyl) aminomethyl] tolutriazole, 1- [N, N-bis (2-ethylhexyl) aminomethyl] carboxybenzotriazole, 1- [N, N-bis (2- Hydroxyethyl) -aminomethyl] benzotriazole, 1- [N, N-bis (2-hydroxyethyl) -aminomethyl] tolutriazole, 1- [N, N-bis ( 2-hydroxyethyl) -aminomethyl] carboxybenzotriazole, 1- [N, N-bis (2-hydroxypropyl) aminomethyl] carboxybenzotriazole, 1- [N, N-bis (1-butyl) aminomethyl] carboxybenzotriazole, 1 -[N, N-bis (1-octyl) aminomethyl] carboxybenzotriazole, 1- (2 ', 3'-di-hydroxypropyl) benzotriazole, 1- (2', 3'-di-carboxyethyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-third-butylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-pentylphenyl) benzotriazole, 2- (2'-hydroxy-4'-octyloxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-third Butylphenyl) benzotriazole, 1-hydroxybenzotriazole-6-carboxylic acid, 1-oleylbenzobenzotriazole, 1,2,4-triazole-3-ol, 5-amino -3-mercapto-1,2,4-triazole, 5-amino-1,2,4-triazole-3-carboxylic acid, 1,2,4-triazole-3-carboxamide, 4- Aminoureazole, 1,2,4-triazol-5-one and a mixture of two or more of these. (C) The component is particularly preferably a benzotriazole-based compound such as benzotriazole or benzotriazole substituted with an alkyl group, a carboxyl group, or a nitro group, and more preferably selected from benzotriazole and tolutriazole. At least one benzotriazole compound in the group consisting of carboxybenzotriazole, nitrobenzotriazole, and 1H-benzotriazole-5-carboxylic acid methyl ester.

The content of the component (C) is an amount in the range of 1 ppm to 0.5%, and preferably an amount in the range of 5 ppm to 0.3% or 10 ppm to 0.1% based on the composition. The reason is that if the content of the component (C) is above the lower limit of the above range, peeling caused by moisture absorption reflow can be sufficiently suppressed; on the other hand, if it is below the upper limit of the above range, the hardened product obtained The mechanical properties are relatively good.

(D) A component is a metal-type condensation reaction catalyst which provides peeling resistance to the hardened | cured material of this composition. Examples of the component (D) include organic aluminum compounds, organic titanium compounds, organic zirconium compounds, organic magnesium compounds, organic zinc compounds, organic copper compounds, organic nickel compounds, organic chromium compounds, organic cobalt compounds, organic iron compounds, and organic compounds. Indium compounds, organic lanthanum compounds, organic tin compounds, organic rhenium compounds, and mixtures of two or more of these. Examples of the organoaluminum compound include alkoxy compounds such as trimethoxyaluminum, triethoxyaluminum, isopropoxyaluminum, isopropoxydiethoxyaluminum, and tributoxyaluminum; triethoxyfluoride Alkyloxy compounds such as aluminum, aluminum tristearate, aluminum tributyrate; aluminum isopropoxide, aluminum second butyrate, aluminum third butyrate, aluminum triacetate, ethyl triacetate Acetoacetone) aluminum, Aluminum triethylacetate, tris (n-propylacetate) aluminum, tris (isopropylacetate) aluminum, tris (n-butylacetate) aluminum, aluminum trisalicylaldehyde, tris (2 -Chelating compounds such as ethoxycarbonylphenol) aluminum and tris (acetamidineacetone) aluminum. Examples of the organic titanium compound include tetraalkoxy titanium such as tetraethoxy titanium, tetra isopropoxy titanium, and tetrabutoxy titanium; tetraethylene glycol titanate; and di-n-butylbis (triethanolamine). Titanate, Titanium Diisopropoxy Bis (Ethylacetone) Acid, Titanium Isopropoxy Caprylate, Titanium Isopropyl Trimethacrylate, Titanium Isopropyl Triacrylate, Isopropyl Triisostearyl Titanate, Isopropyltridecylbenzenesulfonyl titanate, Isopropyltri (butyl, methylpyrophosphinooxy) titanate, Tetraisopropylbis (dilauryl phosphite) (Ethoxy) titanate, dimethyl propylene ethoxy acetate titanate, dipropylene ethoxy acetate titanate, bis (dioctylphosphoryloxy) ethylene titanate, Tris (dioctyl phosphoric acid) titanium isopropoxide, isopropyl tris (dioctyl pyrophosphonium oxy) titanate, tetraisopropyl bis (dioctyl phosphorous phosphonium oxy) titanate, Tetraoctyl bis (di-tridecylphosphinofluorenyloxy) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (di-tridecylphosphite) (Methoxy) titanate, bis (dioctylpyrophosphinooxy) glycolate titanate, tris (dioctylpyrophosphinooxy) Acid ethylene ester, isopropyltri-n-dodecylbenzenesulfonyl titanate, isopropyltrioctylfluorenyl titanate, isopropyldimethylpropenylisostearyltitanate, isopropyl Propyl isostearyl diacryl fluorenyl titanate, isopropyl tris (dioctylphosphonium oxy) titanate, isopropyl tricumyl phenyl titanate, isopropyl tris (N-aminoethyl-aminoethyl) titanate. Examples of the organic zirconium compound include zirconium n-propoxide, zirconium n-butoxide, zirconium tert-butoxide, zirconium isopropoxide, zirconium ethoxylate, zirconyl acetate, zirconium acetoacetone, and butoxy Zirconium acetoacetone, zirconium acetoacetone, zirconium acetoacetate, zirconium acetoacetate, zirconium acetoacetate, zirconium hexafluoroacetonate, zirconium hexafluoroacetonate, zirconium trifluoroacetonate, zirconium trifluoroacetonate. Examples of the organomagnesium compound include ethyl acetoacetate magnesium monoisopropyl, bis (ethyl acetoacetate) magnesium, ethyl acetoacetate magnesium monoisopropyl, and bis (ethyl acetone) magnesium. Examples of the organic zinc compound include zinc bis (ethyl acetate), zinc acetamidine, zinc bis-2-ethylhexanoate, zinc (meth) acrylate, zinc neodecanoate, zinc acetate, zinc octoate, Zinc salicylate. Examples of the organic copper compound include: Ethyl acetate) copper, bis (acetamidineacetone) copper. Examples of the organic nickel compound include bis (ethylacetate) nickel and bis (ethylacetone) nickel. Examples of the organic chromium compound include chromium tris (acetamidineacetate) chromium and tris (acetamidineacetone) chromium. Examples of the organic cobalt compound include cobalt tris (acetamidineacetate) cobalt and tris (acetamidineacetone) cobalt. Examples of the organic iron compound include tris (acetamidineacetate) iron and tris (acetamidineacetone) iron. Examples of the organic indium compound include tris (acetamidoacetate) indium and tris (acetamidoacetone) indium. Examples of the organic lanthanum compound include lanthanum tris (acetamidineacetate) and lanthanum tris (acetamidineacetone). Examples of the organotin compound include tetrakis (acetamidineacetate) tin and tetrakis (acetamidineacetone) tin. Examples of the organic fluorene compound include fluorene n-butoxide, fluorene tertiary butyl oxide, fluorene ethoxide, fluorene isopropoxide, isopropyl alcohol fluorene monoisopropyl ester, acetone acetone fluorene, tetrakis (dimethylformate Amino)). The component (D) is particularly preferably at least one metal-based condensation reaction catalyst selected from the group consisting of an organic aluminum compound, an organic titanium compound, an organic zirconium compound, an organic zinc compound, and an organic iron compound.

The content of the component (D) is an amount within a range of 20 ppm to 0.1%, preferably an amount within a range of 30 ppm to 0.05% or within a range of 50 ppm to 0.03%, relative to the composition. The reason is that if the content of the component (D) is above the lower limit of the above range, peeling caused by moisture absorption reflow can be sufficiently suppressed; on the other hand, if it is below the upper limit of the above range, the obtained Storage stability of the composition.

The (E) component is a catalyst for a hydrosilylation reaction for promoting hardening of the composition. Examples of the (E) component include platinum group element catalysts and platinum group element compound catalysts. Specifically, platinum group catalysts, rhodium catalysts, palladium catalysts, and combinations of at least two of these are exemplified. In particular, a platinum-based catalyst is preferred because it can significantly promote hardening of the composition. Examples of the platinum-based catalyst include platinum fine powder, platinum black, chloroplatinic acid, an alcohol-modified product of chloroplatinic acid, a complex of chloroplatinic acid and a diene, a platinum-olefin complex, and a bis ( Acetylacetate) platinum, bis (acetamidineacetone) platinum and other platinum-carbonyl complexes; chloroplatinic acid-divinyltetramethyldisilaxane complexes, chloroplatinic acid-tetravinyltetramethyl ring Chloroplatinic acid-alkenyl siloxane complexes such as tetrasiloxane; Platinum-alkenylsiloxane complexes, such as platinum-divinyltetramethyldisilaxane complex, platinum-tetravinyltetramethylcyclotetrasiloxane, etc .; chloroplatinic acid and acetylene alcohol A complex of these types; and a mixture of these two or more kinds, especially in terms of promoting the hardening of the composition, is preferably a platinum-alkenyl siloxane complex.

Examples of the alkenylsiloxane used in the platinum-alkenylsiloxane complex include 1,3-divinyl-1,1,3,3-tetramethyldisilazane, 1,3 , 5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, an alkenyl group in which a part of the methyl group of the alkenylsiloxane is substituted by ethyl, phenyl, etc. Siloxane oligomers, and vinyl alkenyl siloxane oligomers in which vinyl is substituted by allyl, hexenyl, etc., especially for the platinum-alkenyl siloxane produced As for the stability of the alkane complex, 1,3-divinyl-1,1,3,3-tetramethyldisilazane is preferred.

In order to improve the stability of the platinum-alkenylsiloxane complex, it is preferable to dissolve these platinum-alkenylsiloxane complexes in 1,3-divinyl-1,1,3, 3-tetramethyldisilaxane, 1,3-diallyl-1,1,3,3-tetramethyldisilaxane, 1,3-divinyl-1,3-dimethyl -1,3-diphenyldisilaxane, 1,3-divinyl-1,1,3,3-tetraphenyldisilaxane and 1,3,5,7-tetramethyl-1 , 3,5,7-tetravinylcyclotetrasiloxane and other alkenyl siloxane oligomers or organic siloxane oligomers such as dimethyl siloxane oligomers, preferably soluble in alkenyl groups Siloxane oligomer.

The content of the component (E) is an amount that promotes the hardening of the composition. Specifically, it is preferred that the catalytic metal atom in the component (E) is within a range of 0.01 to 500 ppm in terms of mass units relative to the composition. The amount is in the range of 0.01 to 100 ppm, or the amount is in the range of 0.1 to 50 ppm. The reason is: if the content of the component (E) is above the lower limit of the above range, the hardenability of the obtained composition is good; on the other hand, if it is below the upper limit of the above range, the color of the hardened product obtained is colored Be suppressed.

In order to prolong the service life at normal temperature and improve the storage stability, (F) a hydrosilylation reaction inhibitor may be contained in the composition. Examples of the component (F) include 1-ethynylcyclohexane-1-ol, 2-methyl-3-butyn-2-ol, and 3,5-dimethyl-1-hexyne-3- Alcohol and 2-phenyl-3-butyne- Alkyne alcohols such as 2-alcohols; alkenyl compounds such as 3-methyl-3-pentene-1-yne and 3,5-dimethyl-3-hexene-1-yne; 1,3,5,7 -Tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane and 1,3,5,7-tetramethyl-1,3,5,7-tetrahexenylcyclotetrasiloxane Methyl alkenyl siloxane oligomers such as alkane; dimethylbis (3-methyl-1-butyne-3-oxy) silane and methylvinylbis (3-methyl-1-butyne -3-oxy) silanes such as alkynyloxysilane; and triallyl isocyanurate compounds.

The content of the (F) component is not limited, but it is preferably within a range of 0.0001 to 5 parts by mass or within a range of 0.01 to 3 parts by mass with respect to 100 parts by mass of the composition.

Moreover, in order to improve the adhesiveness to the base material contacted during hardening, this composition may also contain an adhesion promoter. The adhesion promoter is preferably an organic silicon compound having one or more alkoxy groups bonded to a silicon atom in one molecule. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a methoxyethoxy group, and a methoxy group or an ethoxy group is particularly preferable. Examples of the organic silicon compound other than an alkoxy group bonded to a silicon atom include an alkyl group, an alkenyl group, an aryl group, an aralkyl group, and a halogenated alkyl group. Substituted monovalent hydrocarbon groups; glycidyloxyalkyl groups such as 3-glycidoxypropyl and 4-glycidyloxybutyl; 2- (3,4-epoxycyclohexyl) ethyl and 3- ( Cyclohexylalkyl such as 3,4-epoxycyclohexyl) propyl; Ethoxyalkylene such as 4-oxiranylbutyl and 8-oxiranyloctyl; 3-methyl Acrylic fluorenyloxypropyl and other monovalent organic groups containing propylene fluorenyl groups; isocyanate groups; isocyanurate groups; and hydrogen atoms. The organosilicon compound preferably has a group capable of reacting with an aliphatic unsaturated hydrocarbon group or a hydrogen atom bonded to a silicon atom in the composition, and more specifically, a compound having an aliphatic bond bonded to a silicon atom. A saturated hydrocarbon group or a hydrogen atom bonded to a silicon atom.

The content of the accelerator is not limited, but it is preferably within a range of 0.01 to 10 parts by mass or within a range of 0.1 to 3 parts by mass relative to 100 parts by mass of the composition.

Moreover, this composition may contain a fluorescent substance as another arbitrary component. Examples of the phosphor include oxide-based phosphors, oxynitride-based phosphors, nitride-based phosphors, sulfide-based phosphors, and the like, which are widely used in light-emitting diodes (LEDs). Oxysulfide-based phosphors include yellow, red, green, and blue light-emitting phosphors and a mixture of at least two of these. Examples of the oxide-based phosphor include yttrium, aluminum, and garnet-based YAG (yttrium aluminum garnet) -based green to yellow light-emitting phosphors containing cerium ions; rhenium and aluminum containing cerium ions TAG (terbium aluminum garnet) garnet-based yellow light-emitting phosphors; and silicate green-yellow light-emitting phosphors containing cerium or europium ions. Examples of the nitrogen oxide-based phosphor include silicon, aluminum, oxygen, and nitrogen-based sialon-based red to green light-emitting phosphors containing erbium ions. Examples of the nitride-based phosphors include calcium, strontium, aluminum, silicon, and nitrogen-based cousin-based red light-emitting phosphors containing thallium ions. Examples of the sulfide-based phosphor include a ZnS-based green light-emitting phosphor containing copper ions or aluminum ions. Examples of the oxysulfide-based phosphor include a Y ₂ O ₂ S-based red light-emitting phosphor containing europium ions.

The content of the phosphor is not particularly limited, and in the present composition, it is preferably within a range of 0.1 to 70% by mass or within a range of 1 to 20% by mass.

In addition, as long as the object of the present invention is not impaired, the composition may contain, as other optional components, one or more inorganic fillers selected from silicon dioxide, glass, alumina, and the like; polysilicon Oxygen rubber powder; resin powder such as silicone resin and polymethacrylate resin; one or more components selected from the group consisting of heat-resistant agents, dyes, pigments, flame retardants, surfactants, solvents, and the like.

The composition is hardened by being left at room temperature or heated, and is preferably heated to harden rapidly. The heating temperature is preferably within a range of 50 to 200 ° C.

The composition is preferably hardened to form a hardened product having a hardness of 15 to 99 or 30 to 95 in a type A durometer specified in JIS K 6253. The reason is that if the hardness of the hardened material of the curable polysiloxane composition is above the lower limit of the above range, it has strength and has excellent protection when used as a sealing material or a covering material for an optical semiconductor device. On the other hand, when it is below the upper limit of the said range, hardened | cured material becomes soft and it is excellent in durability.

Next, the optical semiconductor device of the present invention will be described in detail.

The optical semiconductor device of the present invention is characterized in that the optical semiconductor element is sealed, covered, or adhered by the hardened material of the composition. Examples of the optical semiconductor device include a light emitting diode (LED), a semiconductor laser, a photodiode, a photocrystal, a solid-state imaging device, a light emitting body and a light receiving body for a photocoupler, and a light emitting diode (LED) is particularly preferable. ).

Since light-emitting diodes (LEDs) cause light emission from above, below, and from the left and right sides of light-emitting semiconductor elements, the parts that make up light-emitting diodes (LEDs) do not absorb light well, preferably with higher light transmission or reflectance High material. Therefore, the substrate on which the optical semiconductor element is mounted is also preferably a material having a high light transmittance or a high reflectance. Examples of such substrates on which optical semiconductor devices are mounted include conductive metals such as silver, gold, and copper; non-conductive metals such as aluminum and nickel; PPA (Polyphthalamide) and LCP (Liquid Crystal) Polymer (liquid crystal polymer) and other thermoplastic resins mixed with white pigment; epoxy resin, BT (Bismaleimide Triazine, bismaleimide ) Resin, polyimide resin, and silicone resin containing thermosetting resins such as white pigment; ceramics such as alumina and alumina oxynitride. Since the cured product of the curable polysiloxane composition has good thermal shock resistance to the optical semiconductor element and the substrate, the obtained optical semiconductor device can exhibit good reliability.

A cross-sectional view of a surface-mount LED as an example of the optical semiconductor device of the present invention is shown in FIG. 1. Regarding the LED shown in FIG. 1, an optical semiconductor element 1 is bonded to a lead frame 2, and the optical semiconductor element 1 and the lead frame 3 are wire-bonded by a bonding wire 4. A light reflecting material 5 is formed around the light semiconductor element 1. The light semiconductor element 1 on the inner side of the light reflecting material 5 is sealed by the hardened product 6 of the hardening polysiloxane composition described above.

As a method of manufacturing the surface-mounted LED shown in FIG. 1, the following method can be exemplified: an optical semiconductor element 1 is bonded to a lead frame 2 inside the light reflecting material 5, and the light is bonded by a gold bonding wire 4 The semiconductor element 1 and the lead frame 3 are wire-bonded, and then the optical semiconductor element 1 is resin-sealed with the above-mentioned curable polysiloxane composition.

[Example]

The hardening polysiloxane composition and the optical semiconductor device of the present invention will be described in detail by way of examples and comparative examples. The hardness of the cured product of the curable silicone composition, the initial peeling rate of the cured product of the curable silicone composition, and the peeling rate of the cured product after moisture absorption and reflow were measured as described below.

[hardness]

The hardened polysiloxane composition was press-formed under the conditions of 150 ° C., 1 hour, and a pressure of 5 MPa to produce a sheet-like hardened product. The hardness of the sheet-like hardened material was measured with an A-type hardness tester specified in JIS K 6253.

In addition, an optical semiconductor device shown in FIG. 1 was produced by using a curable polysiloxane composition and heating at 150 ° C. for 1 hour. The peel resistance of the curable polysiloxane composition to the optical semiconductor device was measured as described below.

[Initial peeling rate]

With respect to 20 optical semiconductor devices, the peeling state between the lead frame and the bonding wire and the cured product was observed with an optical microscope, and the peeling ratio (the number of peelings / 20) was set as the peeling rate.

[Peeling rate after moisture absorption reflow]

Store 20 of the above-mentioned optical semiconductor devices in an oven at 85 ° C / 85% RH for 168 hours, and then place them in an oven at 280 ° C for 30 seconds, and then return to room temperature (25 ° C). Observe the lead frame and bonding with an optical microscope The peeling state between the thread and the cured product was set as a peeling ratio (the number of peeled pieces / 20 pieces).

[Examples 1 to 6, Comparative Examples 1 to 8]

The following components were uniformly mixed with the compositions (parts by mass) shown in Tables 1 and 2 to prepare the curable polysiloxane compositions of Examples 1 to 6 and Comparative Examples 1 to 8. In the formula, Vi represents a vinyl group and Me represents a methyl group. In Tables 1 and 2, SiH / Vi represents the total of the hydrogen atoms bonded to the silicon atom in the component (B) and the vinyl group in the component (A) in the curable polysiloxane composition. The total number of moles for 1 mole.

As (A) component, the following components were used. The viscosity is a value at 25 ° C, and was measured using a B-type viscometer according to JIS K7117-1.

(a-1-1) Composition: viscosity 300 mPa‧s, average formula: Me ₂ ViSiO (Me ₂ SiO) ₁₅₀ SiMe ₂ Vi

Dimethylpolysilane blocked at both ends of the indicated molecular chain with dimethylvinylsiloxy (content of vinyl group = 0.48% by mass)

(a-1-2) Composition: viscosity 10,000 mPa‧s, average formula: Me ₂ ViSiO (Me ₂ SiO) ₅₀₀ SiMe ₂ Vi

Dimethylpolysilane blocked at both ends of the indicated molecular chain by dimethylvinylsiloxy (content of vinyl group = 0.15% by mass)

(a-2-1) Component: white solid at 25 ° C, soluble in toluene, average unit formula: (Me ₂ ViSiO _1/2 ) _0.15 (Me ₃ SiO _1/2 ) _0.38 (SiO _4/2 ) _0.47 (HO _1/2 ) _0.01

Organopolysiloxane containing more than two vinyl groups in one molecule (content of vinyl group = 4.2% by mass)

(a-2-2) Component: white solid at 25 ° C, soluble in toluene, average unit formula: (Me ₂ ViSiO _1/2 ) _0.13 (Me ₃ SiO _1/2 ) _0.45 (SiO _4/2 ) _0.42 (HO _1/2 ) _0.01

Organopolysiloxane having more than two vinyl groups in one molecule (content of vinyl group = 3.4% by mass)

As (B) component, the following components were used. The viscosity is a value at 25 ° C, and was measured using a B-type viscometer according to JIS K7117-1.

(b-1) Component: Average formula: Me ₃ SiO (MeHSiO) ₅₅ SiMe ₃

Methylhydropolysiloxane blocked by trimethylsiloxy groups at both ends of the molecular chain with a viscosity of 20mPa‧s (content of hydrogen atoms bonded to silicon atoms = 1.6% by mass)

(b-2) Component: Average formula: Me ₃ SiO (MeHSiO) ₁₅ SiMe ₃

Dimethylsiloxane-methylhydrosilane copolymer blocked by trimethylsiloxy at both ends of the molecular chain with a viscosity of 5mPa‧s (content of hydrogen atom bonded to silicon atom = 1.42% by mass)

As (C) component, the following components were used.

(c-1) Ingredient: benzotriazole

(c-2) Component: Toluotriazole

(c-3) Ingredient: carboxybenzotriazole

As (D) component, the following components were used.

(d-1) Ingredient: ethyl acetate zirconium acetate

(d-2) Ingredient: Isopropyltriisostearylfluorenyl titanate

(d-3) Ingredient: Aluminum aluminum alkoxydiisopropoxide

As component (E), a 1,3-divinyltetramethyldisilaxane complex solution of 1,3-divinyltetramethyldisilanium in platinum (content of platinum metal = about 6000 ppm ).

As (F) component, 1-ethynylcyclohexane-1-ol was used.

From the results of Tables 1 and 2, it can be seen that the cured products of the curable polysiloxane compositions of Examples 1 to 6 have high peel resistance to lead frames or bonding wires in optical semiconductor devices.

[Industrial availability]

The hardenable polysiloxane composition of the present invention can be used as a seal for optical semiconductor devices such as light emitting diodes (LEDs), semiconductor lasers, photodiodes, photovoltaic crystals, solid-state imaging, light emitting bodies for photocouplers, and light receiving bodies. Agent, protective agent or adhesive. The optical semiconductor device of the present invention can be used as an optical semiconductor device for an optical device, an optical device, a lighting device, or a lighting device.

Claims (8)

A hardening polysiloxane composition comprising at least: (A) an organic polysiloxane, which has at least 2 alkenyl groups bonded to silicon atoms in one molecule; (B) an organic hydrogenated polysiloxane, It is a molecule with at least 2 hydrogen atoms bonded to silicon atoms {relative to 1 mol of the alkenyl group bonded to silicon atoms in (A) component, and the hydrogen atom bonded to silicon atoms in this component Amount of 0.1 to 10 moles}; (C) triazole-based compound (relative to the composition, an amount of 1 ppm to 0.5% by mass unit); (D) metal-based condensation reaction catalyst (relative to the present The composition is an amount of 20 ppm to 0.1% by mass unit); and (E) a catalyst for a hydrosilylation reaction (an amount that promotes hardening of the composition). The hardening polysiloxane composition according to claim 1, wherein (A) component is (A-1) and the general formula is: R ¹ ₃ SiO (R ¹ ₂ SiO) _m SiR ¹ ₃ (where R ¹ is the same Different monovalent hydrocarbon groups, in which at least two R ¹ in an molecule are alkenyl groups, and m is an integer of 5 to 1,000) linear organic polysiloxane and / or (A-2) average unit represented by Formula: (R ¹ SiO _3/2 ) _a (R ¹ ₂ SiO _2/2 ) _b (R ¹ ₃ SiO _1/2 ) _c (SiO _4/2 ) _d (XO _1/2 ) _e (where, R ¹ is the same as above, wherein 0.01 to 50 mole% of the total of R ¹ is an alkenyl group, X is a hydrogen atom or an alkyl group, and a, b, c, d, and e satisfy 0 ≦ a ≦ 1.0, 0 ≦ b Branched organic polysiloxane represented by ≦ 1.0, 0 ≦ c <0.9, 0 ≦ d <0.5, 0 ≦ e <0.4, and a + b + c + d = 1.0). The curable polysiloxane composition according to claim 1, wherein the component (C) is a benzotriazole-based compound. The hardening silicone composition according to claim 3, wherein the component (C) is selected from the group consisting of benzotriazole, tolutriazole, carboxybenzotriazole, and 1H-benzotriazole-5-carboxylic acid methyl ester. And at least one benzotriazole compound in the group composed of nitrobenzotriazole. The hardening polysiloxane composition according to claim 1, wherein the component (D) is at least one organic compound selected from the group consisting of an organoaluminum compound, an organotitanium compound, an organozirconium compound, an organozinc compound, and an organoiron compound. Metal compounds. The curable polysiloxane composition according to claim 1, which is a sealant or coating agent for an optical semiconductor device. An optical semiconductor device in which the optical semiconductor element is sealed or coated with a hardened material of a hardenable polysiloxane composition according to any one of claims 1 to 5. The optical semiconductor device according to claim 7, wherein the optical semiconductor element is a light emitting diode.